The oil is the major source of energy used by man. The hydrocarbons are used as raw material for several products as well as fuel for vehicles. The transport of such products is done by transport vehicles, such as ships and trucks, as well as via pipelines. Within this perspective, environmental accidents involving oil spills become worrisome seeing that oil products represent a risk to human health, biodiversity and the environment. Therefore, the Environmental Sensitivity Index (ESI) is presented as an interesting tool for environmental management. The Environmental Sensitivity Index to oil appears as a technical-management tool to aid decision-making in the event of accidents involving oil spills because it indicates regions with greater sensitivity to the oil and therefore the locations where the removal and cleaning procedures should be prioritized. Accordingly, the main objective of this paper is to demonstrate the efficiency of remote sensing and GIS in the development of environmental sensitivity index to oil using appropriate geotechnologies to determine and map the sensitivity to oil of a Washington Luís Highway stretch (SP 310) demonstrating the applicability of these tools for the development of ESI for highways. Despite of the great number of accidents envolving oil spills, there is a lack of studies concerning the mapping of the sensitivity to oil for roads and its surroundings